Substrate and catalyst effects in C-H insertion reactions of α-diazoacetamides

Intramolecular C–H insertion reactions of α-diazocarbonyl compounds typically proceed with preferential five-membered ring formation. However, the presence of a heteroatom such as nitrogen can activate an adjacent C–H site toward insertion resulting in regiocontrol issues. In the case of α-diazoacetamide derivatives, both β- and γ-lactam products are possible owing to this activating effect. Both β- and γ-lactam products are powerful synthetic building blocks in the area of organic synthesis, as well as a common scaffold in a range of natural and pharmaceutical products and therefore C–H insertion reactions to form such compounds are attractive processes.

Highly efficient and reusable CNT supported iron(II) catalyst for microwave assisted alcohol oxidation

The highly efficient eco-friendly synthesis of ketones (yields over 99%) from secondary alcohols is achieved by combination of [FeCl2{eta(3)-HC(pz)(3)}] (pz = pyrazol-1-yl) supported on functionalized multi-walled carbon nanotubes and microwave irradiation, in a solvent-free medium. The carbon homoscorpionate iron(II) complex is the first one of this class to be used as catalyst for the oxidation of alcohols.

Adobe's Acrobat -- the Electronic Journal Catalyst?

Adobe's Acrobat software, released in June 1993, is based around a new Portable Document Format (PDF) which offers the possibility of being able to view and exchange electronic documents, independent of the originating software, across a wide variety of supported hardware platforms (PC, Macintosh, Sun UNIX etc.). The principal features of Acrobat are reviewed and its importance for libraries discussed in the context of experience already gained from the CAJUN project (CD-ROM Acrobat Journals Using Networks). This two-year project, funded by two well-known journal publishers, is investigating the use of Acrobat software for the electronic dissemination of journals, on CD-ROM and over networks.

Recovery of palladium from a spent automobile catalyst leaching solution by a thiodiglycolamide derivative

In the sequence of previous research on the development of novel liquid-liquid amidetype compounds to efficiently and selectively extract platinum-group metals (PGMs) from concentrated hydrochloric acid media, a specific thiodiglycolamide derivative – N,N’-dimethyl-N,N’-dicyclohexylthiodiglycolamide (DMDCHTDGA) – has been applied for the recovery of palladium(II) from a spent automobile catalyst leaching solution, containing palladium(II) and rhodium(III) as PGMs. The results obtained are rather promising, since the DMDCHTDGA behavior towards the two PGMs is similar to that observed for hydrochloric acid aqueous media studied before, simulating the real leaching phases. Within eleven metal elements co-existing in solution, the majority in high fold-excesses, only aluminum(III) and cerium(III) interfere in the palladium(II) liquid-liquid extraction process, requiring further optimization.

Toxic metal recovery from spent hydroprocessing catalyst

Spent hydroprocessing catalysts (HPCs) are solid wastes generated in refinery industries and typically contain various hazardous metals, such as Co, Ni, and Mo. These wastes cannot be discharged into the environment due to strict regulations and require proper treatment to remove the hazardous substances. Various options have been proposed and developed for spent catalysts treatment; however, hydrometallurgical processes are considered efficient, cost-effective and environmentally-friendly methods of metal extraction, and have been widely employed for different metal uptake from aqueous leachates of secondary materials. Although there are a large number of studies on hazardous metal extraction from aqueous solutions of various spent catalysts, little information is available on Co, Ni, and Mo removal from spent NiMo hydroprocessing catalysts. In the current study, a solvent extraction process was applied to the spent HPC to specifically remove Co, Ni, and Mo. The spent HPC is dissolved in an acid solution and then the metals are extracted using three different extractants, two of which were aminebased and one which was a quaternary ammonium salt. The main aim of this study was to develop a hydrometallurgical method to remove, and ultimately be able to recover, Co, Ni, and Mo from the spent HPCs produced at the petrochemical plant in Come By Chance, Newfoundland and Labrador. The specific objectives of the study were: (1) characterization of the spent catalyst and the acidic leachate, (2) identifying the most efficient leaching agent to dissolve the metals from the spent catalyst; (3) development of a solvent extraction procedure using the amine-based extractants Alamine308, Alamine336 and the quaternary ammonium salt, Aliquat336 in toluene to remove Co, Ni, and Mo from the spent catalyst; (4) selection of the best reagent for Co, Ni, and Mo extraction based on the required contact time, required extractant concentration, as well as organic:aqueous ratio; and (5) evaluation of the extraction conditions and optimization of the metal extraction process using the Design Expert® software. For the present study, a Central Composite Design (CCD) method was applied as the main method to design the experiments, evaluate the effect of each parameter, provide a statistical model, and optimize the extraction process. Three parameters were considered as the most significant factors affecting the process efficiency: (i) extractant concentration, (ii) the organic:aqueous ratio, and (iii) contact time. Metal extraction efficiencies were calculated based on ICP analysis of the pre- and post–leachates, and the process optimization was conducted with the aid of the Design Expert® software. The obtained results showed that Alamine308 can be considered to be the most effective and suitable extractant for spent HPC examined in the study. Alamine308 is capable of removing all three metals to the maximum amounts. Aliquat336 was found to be not as effective, especially for Ni extraction; however, it is able to separate all of these metals within the first 10 min, unlike Alamine336, which required more than 35 min to do so. Based on the results of this study, a cost-effective and environmentally-friendly solventextraction process was achieved to remove Co, Ni, and Mo from the spent HPCs in a short amount of time and with the low extractant concentration required. This method can be tested and implemented for other hazardous metals from other secondary materials as well. Further investigation may be required; however, the results of this study can be a guide for future research on similar metal extraction processes.

The effects of PVP(FE(III)) catalyst and polymer molecular weight on gene delivery via biodegradable crosslinked polyethylenimine

Human gene therapy has faced many setbacks due to the immunogenicity and oncogenity of viruses. Safe and efficient alternative gene delivery vehicles are needed to implement gene therapy in clinical practice. Polymeric vectors are an attractive option due to their availability, simple chemistry, and low toxicity and immunogenicity. Our group has previously reported biodegradable polyethylenimines (PEI) that show high transfection efficiency and low toxicity by cross-linking 800 Da PEI with diacrylate cross-linkers using Michael addition. However, the synthesis was difficult to control, inconsistent, and resulted in polymers with a narrow range of molecular weights. In the present work, we utilized a heterogenous PVP(Fe(III)) catalyst to provide a more controllable PEI crosslinking reaction and wider range of biodegradable PEIs. The biodegradable PEIs reported here have molecular weights ranging from 1.2 kDa to 48 kDa, are nontoxic in MDA-MB-231 cells, and show low toxicity in HeLa cells. At their respective optimal polymer:DNA ratios, these biodegradable PEIs demonstrated about 2-5-fold higher transfection efficiency and 2-7-fold higher cellular uptake, compared unmodified 25 kDa PEI. The biodegradable PEIs show similar DNA condensation properties as unmodified PEI but more readily unpackage DNA, based on ethidium bromide exclusion and heparan sulfate competitive displacement assays, which could contribute to their improved transfection efficiency. Overall, the synthesis reported here provides a more robust, controlled reaction to produce cross-linked biodegradable PEIs that show enhanced gene delivery, low toxicity, and high cellular uptake and can potentially be used for future in vivo studies.

Biodiesel a partir de óleos de alta acidez: desenvolvimento de um processo catalítico homogêneo

O presente trabalho visa o desenvolvimento de um processo para a produção de biodiesel partindo de óleos de alta acidez, aplicando um processo em duas etapas de catálise homogênea. A primeira é a reação de esterificação etílica dos ácidos graxos livres, catalisada por H2SO4, ocorrendo no meio de triglicerídeos e a segunda é a transesterificação dos triglicerídeos remanescentes, ocorrendo no meio dos ésteres alquílicos da primeira etapa e catalisada com álcali (NaOH) e álcool etílico ou metílico. A reação de esterificação foi estudada com uma mistura modelo consistindo de óleo de soja neutro acidificado artificialmente com 15%p de ácido oleico PA. Este valor foi adotado, como referência, devido a certas gorduras regionais (óleo de mamona advinda de agricultura familiar, sebos de matadouro e óleo de farelo de arroz, etc.) apresentarem teores entre 10-20%p de ácidos graxos livres. Nas duas etapas o etanol é reagente e também solvente, sendo a razão molar mistura:álcool um dos parâmetros pesquisados nas relações 1:3, 1:6 e 1:9. Outros foram a temperatura 60 e 80ºC e a concentração percentual do catalisador, 0,5, 1,0 e 1,5%p, (em relação à massa de óleo). A combinatória destes parâmetros resultou em 18 reações. Dentre as condições reacionais estudadas, oito atingiram acidez aceitável inferior a 1,5%p possibilitando a definição das condições para aplicação ótima da segunda etapa. A melhor condição nesta etapa ocorreu quando a reação foi conduzida a 60°C com 1%p de H2SO4 e razão molar 1:6. No final da primeira etapa foram realizados tratamentos pertinentes como a retirada do catalisador e estudada sua influência sobre a acidez final, utilizando-se de lavagens com e sem adição de hexano, seguidas de evaporação ou adição de agente secante. Na segunda etapa estudaram-se as razões molares de óleo:álcool de 1:6 e 1:9 com álcool metílico e etílico, com 0,5 e 1%p de NaOH assim como o tratamento da reação (lavagem ou neutralização do catalisador) a 60°C, resultando em 16 experimentos. A melhor condição nesta segunda etapa ocorreu com 0,5%p de NaOH, razão molar óleo:etanol de 1:6 e somente as reações em que se aplicaram lavagens apresentaram índices de acidez adequados (<1,0%p) coerentes com os parâmetros da ANP.

Catalyst: Architecture for Change and Social Justice

In major cities today, there are neighborhoods that have been continually underserved and as a result are in decay. Private investors and developers turn to these particular neighborhoods, propose large developments that gentrify these areas, displacing communities and with them their social, political, and economic issues. The purpose of this thesis is to analyze South West, Baltimore, a community composed of 8 neighborhoods on the verge of being gentrified, by incoming development. Through investigating the key issues present in this community for many years, this thesis will attempt to develop a catalytic environment, which will facilitate change within the community by providing a place for its members to help tackle these issues, improving their circumstances, and the circumstances of the neighborhoods they form part of.

Urban Catalyst: Continuing the Legacy of Massachusetts Avenue

This thesis proposes a reconnection of Massachusetts Avenue to the Anacostia River waterfront in Washington, DC. An intervention at the site of Reservation 13 will reconcile a difficult urban edge and reunite the neighborhood of Lincoln Park with the river. It also addresses the discontinuity of the avenue to the southeast and proposes the development of a bridge between the Western bank and ultimately Randle Circle. Along this reconciled corridor will be a series of architectural interventions that serve to promote community involvement. Ultimately this thesis is about generating an urban continuity and the cultural vibrancy and understanding that such a connection would foster.

Motivic Decomposition of Projective Pseudo-Homogeneous Varieties

Let G be a semi-simple algebraic group over a field k. Projective G-homogeneous varieties are projective varieties over which G acts transitively. The stabilizer or the isotropy subgroup at a point on such a variety is a parabolic subgroup which is always smooth when the characteristic of k is zero. However, when k has positive characteristic, we encounter projective varieties with transitive G-action where the isotropy subgroup need not be smooth. We call these varieties projective pseudo-homogeneous varieties. To every such variety, we can associate a corresponding projective homogeneous variety. In this thesis, we extensively study the Chow motives (with coefficients from a finite connected ring) of projective pseudo-homogeneous varieties for G inner type over k and compare them to the Chow motives of the corresponding projective homogeneous varieties. This is done by proving a generic criterion for the motive of a variety to be isomorphic to the motive of a projective homogeneous variety which works for any characteristic of k. As a corollary, we give some applications and examples of Chow motives that exhibit an interesting phenomenon. We also show that the motives of projective pseudo-homogeneous varieties satisfy properties such as Rost Nilpotence and Krull-Schmidt.

Synthesis of waterborne polyurethane-urea dispersions with chain extension step in homogeneous and heterogeneous media

Hypothesis: The possibility of tailoring the final properties of environmentally friendly waterborne polyurethane and polyurethane-urea dispersions and the films they produce makes them attractive for a wide range of applications. Both the reagents content and the synthesis route contribute to the observed final properties. Experiments: A series of polyurethane-urea and polyurethane aqueous dispersions were synthesized using 1,2-ethanediamine and/or 1,4-butanediol as chain extenders. The diamine content was varied from 0 to 4.5 wt%. Its addition was carried out either by the classical heterogeneous reaction medium (after phase inversion step), or else by the alternative homogeneous medium (prior to dispersion formation). Dispersions as well as films prepared from dispersions have been later extensively characterized. Findings: 1,2-Ethanediamine addition in heterogeneous medium leads to dispersions with high particle sizes and broad distributions whereas in homogeneous medium, lower particle sizes and narrow distributions were observed, thus leading to higher uniformity and cohesiveness among particles during film formation. Thereby, stress transfer is favored adding the diamine in a homogeneous medium; and thus the obtained films presented quite higher stress and modulus values. Furthermore, the higher uniformity of films tends to hinder water molecules transport through the film, resulting, in general, in a lower water absorption capacity.

Environmental assessment of proton exchange membrane fuel cell platinum catalyst recycling

International audience

The temporal evolution of the energy flux across scales in homogeneous turbulence

A temporal study of energy transfer across length scales is performed in 3D numerical simulations of homogeneous shear flow and isotropic turbulence. The average time taken by perturbations in the energy flux to travel between scales is measured and shown to be additive. Our data suggests that the propagation of disturbances in the energy flux is independent of the forcing and that it defines a ‘velocity’ that determines the energy flux itself. These results support that the cascade is, on average, a scale-local process where energy is continuously transmitted from one scale to the next in order of decreasing size.

Direct numerical simulation of statistically stationary and homogeneous shear turbulence and its relation to other shear flows

Statistically stationary and homogeneous shear turbulence (SS-HST) is investigated by means of a new direct numerical simulation code, spectral in the two horizontal directions and compact-finite-differences in the direction of the shear. No remeshing is used to impose the shear-periodic boundary condition. The influence of the geometry of the computational box is explored. Since HST has no characteristic outer length scale and tends to fill the computational domain, long-term simulations of HST are “minimal” in the sense of containing on average only a few large-scale structures. It is found that the main limit is the spanwise box width, Lz, which sets the length and velocity scales of the turbulence, and that the two other box dimensions should be sufficiently large (Lx ≳ 2Lz, Ly ≳ Lz) to prevent other directions to be constrained as well. It is also found that very long boxes, Lx ≳ 2Ly, couple with the passing period of the shear-periodic boundary condition, and develop strong unphysical linearized bursts. Within those limits, the flow shows interesting similarities and differences with other shear flows, and in particular with the logarithmic layer of wall-bounded turbulence. They are explored in some detail. They include a self-sustaining process for large-scale streaks and quasi-periodic bursting. The bursting time scale is approximately universal, ∼20S−1, and the availability of two different bursting systems allows the growth of the bursts to be related with some confidence to the shearing of initially isotropic turbulence. It is concluded that SS-HST, conducted within the proper computational parameters, is a very promising system to study shear turbulence in general.